Carbonaceous adsorbents from pyrolyzed polysulfonated polymers

ABSTRACT

Carbonaceous adsorbent particles having multimodal pore size, including micropores and macropores, with improved adsorptive and separative properties, are prepared by partial pyrolysis of polysulfonated macroporous precursor resins, said resins being in turn derived from macroporous poly(vinylaromatic) resins. The particles may be further treated by activating with reactive gases or by functionalization.

This is a division of allowed Ser. No. 519,040, filed May 4, 1990,which, in turn, is a division of Ser. No. 307,554, filed Feb. 7, 1989,now U.S. Pat. No. 4,957,897, which, in turn, is a division of Ser. No.150,183, filed Jan. 29, 1988, now U.S. Pat. No. 4,839,331.

This invention relates to adsorbent particles, and more particularly topartially pyrolyzed particles prepared from macroporous polysulfonatedpolymers. It further relates to a process for making such partiallypyrolyzed particles, a process for their further activation andfunctionalization, and the use of such particles as components ofseparative and adsorptive systems.

BACKGROUND OF THE INVENTION

The high surface and internal areas of activated carbon have made ituseful in many separative, adsorptive, and purification processes.Preparation of improved carbonaceous adsorbents by pyrolysis ofsynthetic resins, such as crosslinked polystyrene, or of polymerstreated with oxidants to increase the yield of carbonaceous product, hasbeen known for some years. Useful adsorbents from partially pyrolyzedporous precursors, especially those based on crosslinked, stabilized(treated with fixatives or oxidants to prevent depolymerization)polyvinyl aromatics, represent an improved version of such materials.Neely, U.S. Pat. No. 4,040,990, which is hereby incorporated into thepresent specification by reference, and in Carbon, 19, 27 (1981),describes controlled partial pyrolysis of macroporous monosulfonated (orotherwise fixated) polystyrene to produce charred beads maintaining themacroporous structure of the precursor polymer but with microporositycreated during heat treatment. Neely further teaches adsorptive andpurification uses for such pyrolyzed polymers; see also U.S. Pat. No.4,063,912 and U.S. Pat. No. 4,267,055. The term "carbonaceous adsorbent"as used herein refers to particles prepared by the process of Neely fromsulfonated macroporous polystyrene resins.

During the many years of research on polystyrenebased cation exchangeresins based on the introduction of sulfonic acid by sulfonation withsulfuric acid or chlorosulfonic acid, methods have been found toincrease the resin capacity by introduction of more than one sulfonicacid per aromatic ring. Methods for polysulfonation are taught, interalia, by Corte et al., U.S. Pat. No. 3,158,583, for conventional,nonmacroporous resins.

There is little specific information in the art as to preparation ofpolysulfonated macroporous resins, although such have been marketed anddescribed in the trade literature. U.S. Pat. No. 4,224,415 claims aprocess for sulfonating macroporous polymers with a sulfonating agentselected from the group of concentrated sulfuric acid, oleum, sulfurtrioxide, and chlorosulfonic acid. It fails to teach that polysulfonatedresins result from such a sulfonation, nor does it teach any advantagesfor the resulting resins.

British Patent No. 1,525,420, in a broad description of method forrendering infusible various porous high molecular weight compounds(including macroporous resins), and then calcining them, relatestechniques for polysulfonation earlier described by Corte et al. amongthose suitable for creating infusibility. No characterization data aregiven for the polymer prior to calcination. Preferred infusibilityreactants are sulfur trioxide, sulfuric acid, or chlorosulfonic acid.This reference discloses pyrolysis of macroporous resins treated with15% fuming sulfuric acid and pyrolyzed, and describes an experimentalmethod for determining the porosity of the pyrolyzed material down to2-5 nm. The results described in the tables of the reference show theabsence of any porosity development below 5 nm, and multimodal porosityis not taught. In contrast, Neely in the cited references fully showsthe development of microporosity for monosulfonated macroporous resins.Further, the British patent is silent about the processing advantagesobserved in pyrolysis of polysulfonated resins.

Japanese Kokai 52-30800, filed at the same time and by the sameapplicant as British 1,525,420, teaches broadly and with very limitedexemplification several methods for making macroporous resins and alarge variety of methods for making the porous polymer infusible,including but not distinguishing sulfuric acid, sulfuric acid anhydride,sulfur dioxide, and chlorosulfonic acid. A polystyrene in whichmicropores are produced by extraction of a water-soluble polymer isexemplified as being treated with fuming 15% sulfuric acid at 80° C. foran unknown time and pyrolyzed, but the data show no microporedevelopment below 15 nm.

Japanese Kokai 53-50088, to the same applicant as British 1,525,420 andKokai 52-30800, teaches preparation of improved adsorbents by pyrolyzinginfusible resins made from monomer mixtures containing multiple,non-conjugated, ethylenically unsaturated groups by suspensionpolymerization in the presence of a precipitant liquid that is a solventfor the monomers and does not swell the polymer. The porous resin soproduced is made infusible by a process such as sulfonation or nitrationand then pyrolyzed. It is stated that the method can be used to producepore volumes of 0.1 cc/g., preferably 0.3 cc/g and pore sizes of 1 to5000 nm, preferably 5 to 1000 nm. The single experiment reported teachespreparation of a non-macroporous (gellular) styrene/divinylbenzenecopolymer, sulfonation for six hours at 110° C. with 15% fuming sulfuricacid, and pyrolysis at a temperature of 1000° C., achieved by heatingunder nitrogen gas at a rate of 300° C./hour. The resulting resin wasreported to have an average pore diameter of 20 nm and 0.6 cc/g of poreswith diameters of 5 nm or more, with no mention of smaller pore sizes orof macropores. Activation of the pyrolyzed resin with steam at 800° C.to yield a resin with a surface area of 1100 m² /g. is noted. There isno direct demonstration in the patent that pore sizes and adsorptivebehavior of the present invention can be achieved, as there is noexemplification of polysulfonation conditions being preferred, or ofsuch being applied to a macroporous resin.

In Japanese Kokai 62-197308 is taught a method for producing a porouscarbon material having a large void fraction by pyrolysis of asynthetic, crosslinked, styrene-divinylbenzene polymer which has beenwetted with concentrated sulfuric acid under reduced pressure and thencarbonized in an inactive gas stream.

In Japanese Patent Application 62-76093, filed Mar. 31, 1987, is taughtthe use of commercially available macroporous resins from Rohm and HaasCo. prepared by the method of Neely for the removal of pyrogens fromwater. The examples are merely duplicates of those examples presented inBritish Patent 1,525,420 discussed above and shown not to produce amicroporous structure, except that the newer application furtherdiscloses further activation by steam for two hours at 800° C., withresults exactly those disclosed in Japanese Kokai 53-50088.

THE INVENTION

We have discovered adsorbent particles having high surface area and aminimum volume contributed by micropores of about 0.02 cm³ /g,preferably about 0.05 cm³ /g, and more preferably about 0.1 cm³ /g,which particles are made by the partial pyrolysis of microporous,polysulfonated resins. We have further discovered a process by whichthese adsorbent particles are made, which process comprises partiallypyrolyzing, in an inert atmosphere, at temperatures from about 300° toabout 1200° C., polysulfonated, macroporous, vinylaromatic copolymers.We have further discovered an embodiment of the present invention inwhich the partially pyrolyzed adsorbent particles are activated byheating in an activating atmosphere. We have discovered that theseadsorbent particles are useful for adsorption of gases, vapors, liquidsand the like onto their surfaces, for such purposes as purification,removal and separation, including chromatographic separation, and thatthey are also useful for the preparation of functionalized resinparticles by subjecting them to known functionalization reactions.

As used herein, macroporous copolymers include macroporous ormacroreticular copolymers prepared by suspension polymerization in thepresence of a precipitant, as described in U.S. Pat. No. 4,256,840 andU.S. Pat. No. 4,224,415, and copolymers into which large pores have beenintroduced by other methods as for example the technique described inU.S. Pat. No. 3,122,514. The resins prepared from macroporous copolymersare called macroporous resins. Polysulfonation, as used herein, refersto a sulfonation process that is sufficiently vigorous to introduce anaverage of more than one sulfonate group per accessible aromaticnucleus. Such vigorous sulfonation is accompanied by the formation of asignificant number of sulfone crosslinks, in which sulfonate groupsbridge between two aromatic nuclei to form --SO₂ -- crosslinks.

The vinyl aromatic polymers of the present invention are those in whichat least 50% of the units contain a vinylaromatic group. Preferred arevinylaromatic polymers in which at least 90% of the units contain avinylaromatic group. Especially preferred are vinylaromatic polymerswhere at least 98% of the units contain a vinylaromatic group.Vinylaromatic monomers include, among others, styrene,alpha-methylstyrene, vinyltoluene, p-methylstyrene, ethyl-vinylbenzene,vinylnaphthalene, divinylbenzene, trivinylbenzene,vinylisopropenylbenzene, diisopropenylbenzene, and the like. Especiallypreferred are styrene and divinylbenzene (which will normally containsome ethylvinylbenzene).

As the polysulfonation produces both sulfonate and sulfone groups,analytical identification of the polysulfonated resin is best done byconventional microanalytical procedures for elemental sulfur content. Apolysulfonated resin, as used herein, is one in which themicroanalytical value for sulfur introduced into the resin molecularstructure by the sulfonation process is at least 1.04 times, preferablyat least 1.07 times, and more preferably at least 1.16 times the valuefor the sulfur so introduced by conventional, sulfuric acid sulfonation.In general, conventional, sulfuric acid sulfonation of lightlycrosslinked copolymers will introduce approximately the same amount ofsulfur as would theoretically be expected for complete monosulfonationof the copolymer. In highly crosslinked copolymers, however, sulfonationtends to occur predominantly at or near the surface of the copolymerparticle, and to a lesser extent at increasing distances from thesurface. Polysulfonation exhibits a similar phenomenon; a highlycrosslinked, polysulfonated copolymer may contain less sulfur thantheoretically expected for monosulfonation, yet the accessible aromaticnuclei will be polysulfonated.

Sulfone crosslinking occurs under the same vigorous reaction conditionsrequired to achieve polysulfonation, and is therefore present inpolysulfonated resins. The preparation of such resins is described inRomanian Patent No. 56,980 and in U.S. Pat. No. 3,158,583. Besides thetwo-step sulfonations described in these references, the copolymers mayalso be polysulfonated with oleum alone, to obtain a polysulfonatedresin operable in the present invention. Other procedures for preparingpolysulfonated aromatic cation exchange resins will be apparent to thoseskilled in the art. The preferred copolymers to be polysulfonated arethose prepared by polymerizing a monovinyl aromatic monomer, preferablystyrene, and a polyvinyl crosslinking monomer, preferablydiisopropenylbenzene or divinylbenzene, to produce macroporouscopolymers. Particularly preferred are copolymer particles produced inbead form by suspension polymerization, and more particularly preferredare those in which a precipitant such as those taught in U.S. Pat. No.4,256,840 is included in the suspension mixture to produce macroporouspolymer beads.

The polyvinyl crosslinker level in the copolymer may be from about 2% toabout 98% by weight of the copolymer, with the preferred range beingfrom about 3% to about 80% by weight of the copolymer. Suitablecrosslinkers include those discussed by Neely in U.S. Pat. No.4,040,990. Combinations of crosslinkers may also be used.

The precipitant may be present in ratios from about 20 parts per 100parts of monomer to about 600 parts per 100 parts of monomer, dependingon the crosslinking level and precipitant used.

In the present text, the term "macropore" is used to mean pores ofaverage diameter from about 3.5 nm to about 1000 nm, although values ofabout 3.5 nm to about 50 nm are preferred. "Micropore" refers to porevalues of average diameter about 0.10 nm to about 3.5 nm, preferablyabout 0.15 nm to about 2 nm. A sub-category of micropores is"mesopores", which term is used herein to mean pores having an averagediameter from about 0.6 nm to about 3.5 nm.

Although resin beads of the size produced by conventional suspensionpolymerization processes are a useful size for the further reactions andend uses, the process may be conducted on larger or smaller beads, andeven on ground macroporous resins produced in non-bead form. Foradsorbent and separative use, the resins may be further ground orselectively sieved to produce the desired particle size.

A preferred method for conducting the polysulfonation is to contact themacroporous resin with fuming sulfuric acid for a period of from about 5hours to about 20 hours or more at a temperature of from about 100° toabout 150° C. Particularly preferred is treatment at about 120° C. for aperiod of about 16 hours. The fuming sulfuric acid may have a specificgravity of from about 1.88 to about 2.00 and is used in amounts of fromabout 100% to about 2000% or more, based on the weight of themacroporous resin. A preferred set of conditions is to use 20% oleum,specific gravity 1.915, at from about 1400 to about 1500%. Thepolysulfonated resin is preferably hydrated, then washed to remove acidand dried prior to calcining. Care must be taken in the hydration stepnot to shatter the resin by direct contact with water; hydration withdiluted sulfuric acid is preferred.

The pyrolysis may be conducted by any of the methods taught by Neely,U.S. Pat. No. 4040990. Preferred is a controlled pyrolysis attemperatures from about 300° C. to about 1200° C. for a period of about15 minutes to about two hours; in the absence of activating chemicals,the pyrolysis may be maintained longer at the upper temperature withvery little change taking place in weight loss or pore size development.The polymer may be agitated and/or heated with steam or hot gases or maybe heated under static conditions under nitrogen. A fluidized bedtreatment may be used, in which heated nitrogen is passed upward throughthe bed, the gas also serving to agitate the bed particles. The polymermay be introduced directly into the oven at the highest temperaturedesired, or may be heated in several steps to the final temperature.

A distinct advantage in processing the polysulfonated resins of thepresent invention, compared with the monosulfonated resins taught byNeely, is observed in the production of little or no tarry products(which can clog the gas exhaust line and foul the pyrolysis apparatus),and any tars that are produced being of lower molecular weight and thusmore volatile. The resulting pyrolyzed polysulfonated resins exhibitless weight loss than their monosulfonated counterparts under similarpyrolysis conditions, which means the yield of useful carbonaceousmaterial is higher. Without wishing to be bound by theory, it may bethat the improved evolution of gases during pyrolysis may contribute tothe higher pore volume caused by outgassing.

The carbonaceous material produced from the polysulfonated material maybe used as such, or it may be activated further by processes known tothe art such as exposure to various activating gases, including oxygen,steam, water, ammonia, carbon monoxide, carbon dioxide, and the like, attemperatures from about 300° C. to about 1200° C. or more. Activation inthe presence of steam at about 800° C. to about 1000° C. is preferred.

It is also possible to conduct the pyrolysis in the presence of anactivating gas rather than in an inert gas such as nitrogen. Attemperatures below about 800° C., pyrolysis is the kineticallydominating process, and little effect of the activating gas is seen atrelatively short pyrolysis times. At pyrolysis temperatures above about800° C., or with lengthy exposure to the activating gas at temperaturesbetween about 300° C. and about 800° C., both pyrolysis and activationcan be accomplished. Activation with reactive gases is an optionalprocess sometimes desirable for the modification of adsorbentproperties, but is not a necessary part of the invention.

The carbonaceous particles of the present invention may befunctionalized by methods such as taught in Beasley et al., U.S. Pat.No. 4,265,768, which is hereby incorporated into the present disclosureby reference, to incorporate ion exchange functional groups orprecursors thereof; the resulting functionalized particles are useful asion exchange resins.

The particles may be chemically treated to adsorb chemicals which reactwith materials to be separated, so as more cleanly to separate saidmaterials. For example, a resin intended as a solid phase forchromatographic separation may be treated with hydrogen bromide; duringthe separation of ethylene oxide in admixture with other gases theethylene oxide is converted to ethylene bromohydrin, which is readilyseparated and detected.

As will be seen from the examples below, the pyrolyzed polymer particlesof this invention surpass their monosulfonated counterparts in theirability to separate certain mixtures of small molecules; they alsoexhibit a significantly higher volume of micropores, as well as cleanerand larger pore volumes in the macroporous range.

The pyrolyzed polysulfonated polymers of the present invention areuseful in those applications where pyrolyzed resins based onmonosulfonated macroporous resins are useful, such as in thepurification of groundwater, especially for removal of endotoxins astaught in Agui et al., Glossary of Manuscripts for Presentation to theChemical Society of Japan, November, 1987; in the adsorption of noxiousgases; in removal of noxious organic materials; in the separation ofstreams of organic or inorganic gases; in the analysis of such gaseousmixtures, such as mixtures of the noble gases, and the like. Pyrolyzedresins further activated with nitrogen may be useful as supports forcatalysts for chemical reactions, such as molybdenum- based catalystsfor the conversion of asphaltenes.

The following examples are intended to illustrate the invention, and notto limit it except as it is limited in the claims. All percentagesherein are by weight unless otherwise indicated, and all reagents are ofgood commercial quality unless otherwise indicated. As used herein, theabbreviations "cc" and "cm³ " both mean "cubic centimeter".

EXAMPLE 1

This example describes a method for forming a macroporous resin suitablefor polysulfonation and pyrolysis. By methods described in U.S. Pat. No.4,382,124, a macroporous polymer was prepared from styrene containingsufficient commercial divinylbenzene (55% purity) to charge 19.5%divinylbenzene (active). Methyl amyl alcohol, 33.4% on monomer, wasemployed as precipitant. Spherical particles were produced 0.85-2.5 mmin diameter. Such resins typically have a pore diameter range of about60 to about 300 nm, a total porosity of about 0.36 cm³ per gram ofresin, and exhibit little or no microporous or mesoporous structure.

EXAMPLE 2

This comparative example describes conditions for the monosulfonationprocess known in the prior art. By the method taught in Neely, U.S. Pat.No. 4,040,990, the copolymer of Example 1 was treated with 99% sulfuricacid at a weight ratio of 6 parts acid to 1 part resin for three hoursat 122° C., followed by slow dilution with deionized water at 100° C.over three hours. The resin was then further washed with deionized waterand vacuum dried. The sulfur content was 15.85%, or 93.5% of thetheoretical value for complete monosulfonation.

EXAMPLE 3

This example describes conditions for polysulfonation to produce theresins pyrolyzed to form the adsorbents of the present invention. To 120parts of the polymer of Example 1 was added 1720 parts by weight of 20%oleum. The mixture was heated to 120° C. overnight (16 hours). Hydrationof the sulfonated resin was achieved by adding dropwise to the reaction,after cooling to about 100° C., 250 parts of water followed by removalof about 200 parts of liquid. The quench procedure was repeated threetimes. The resin was then washed by addition of 400 parts water withstirring, the liquid removed by suction, and the resin placed in acontainer suitable for containing the resin under a flow of deionizedwater. Water was allowed to flow through the container until color throwwas minimized. The water was then suctioned off, the resin rinsed threetimes with 1000 parts methanol and dried under vacuum at 80° C. Theyield of resin isolated was 298 g. The sulfur content was 20.69%, or122% of the theoretical value for complete monosulfonation.

EXAMPLE 4

This example describes conditions for pyrolysis at 800° C. The polymersof Examples 2 and 3 were pyrolyzed in two different ways which werejudged to be equivalent as determined by BET surface area. The pore sizedistributions were determined as described in the Neely publicationcited above. The BET measurement of surface area/unit weight wasdetermined by mercury porosimetry. The results of the pore sizedistributions in Table 1, below, show the polysulfonated precursors(Examples 4A and 4B) higher pore volumes than do precursors produced bystandard sulfonations (Example 4C and 4D).

The pyrolysis conditions are as follows:

i. A twenty gram sample of sulfonated copolymer was placed in a 2.54 cmquartz tube between two plugs of quartz wool. The tube was purged withnitrogen and the tube place in a tube furnace at ambient temperature.The tube was then heated to 800° C. over approximately 1 hour and thenheld at 800° C. for 1/2 hour. The adsorbent was cooled under nitrogenand then weighed to determine yield.

ii. A twenty gram sample of sulfonated copolymer was placed in a 2.54 cmquartz tube between two plugs of quartz wool. The tube was then purgedwith nitrogen and the tube placed in a tube furnace that had beenpreheated to 500° C. After approximately 1/2 hour, the furnace washeated to 800° C. and held at that temperature for 1/2 hour.

                  TABLE 1                                                         ______________________________________                                        Preparation/  BET      Pore Volume (cc/g)                                     pyrolysis                                                                              Sulfo-   Surface  0.43-  0.6-   3.5-                                 method   nation.sup.1                                                                           (m.sup.2 /g)                                                                           0.6 nm 3.5 nm 30 nm                                ______________________________________                                        4A Ex.3/4(i)                                                                           A        496      0.219  0.0152 0.44                                 4B Ex.3/4(ii)                                                                          A        493      0.221  0.0178 0.42                                 4C Ex.2/4(i)                                                                           B        401      0.108  0.0060 0.35                                 4D Ex.2/4(ii)                                                                          B        402      0.108  0.0038 0.35                                 ______________________________________                                         .sup.1 A = polysulfonation B = monosulfonation                           

It was observed that pyrolysis of the monosulfonated samples wasaccompanied by more non-volatile tar than in the preparation from thepolysulfonated samples; the volatile material separated from thepolysulfonated resin was lower in viscosity than that from themonosulfonated resin.

EXAMPLE 5

This example describes results for pyrolysis of monosulfonated andpolysulfonated resin at 500° C., and also exemplifies pyrolysis of apolysulfonated resin at 1100° C. The resins Examples 2 and 3 werepyrolyzed at 500° C. maximum by the technique of Example 4b, except thetemperature was not taken above 500° C. In a similar manner, sample 5Cwas prepared by pyrolysis of the polysulfonated resin of Example 3 at amaximum temperature of 1100° C. The results of this example are in Table2 below.

                  TABLE 2                                                         ______________________________________                                                Preparative                                                                   pyrolysis   Sulfonation BET Surface                                   Sample  method      Conditions  Area, m.sup.2 /g                              ______________________________________                                        5A      Ex.3/500°                                                                          Polysulfonation                                                                           544                                           5B      Ex.2/500°                                                                          Standard    471                                           5C       Ex.3/1100°                                                                        Polysulfonation                                                                           520                                           ______________________________________                                    

EXAMPLE 6

This example teaches preparation of monosulfonated and polysulfonatedresins from several macroporous precurors. In a manner similar toExample 1, macroporous polymers of styrene and crosslinking monomerswere prepared in the presence of a precipitant. All starting resins hada particle size, as measured by standard screen techniques, which passedthrough a 1.18 mm sieve and was retained on a 0.300-mm sieve. DVB isdivinylbenzene, MAmAlc is methyl amyl alcohol.

The samples were subjected either to the polysulfonation conditions ofExample 3, or the monosulfonation conditions of Example 2. The resultsof this example are in Table 3 below.

                  TABLE 3                                                         ______________________________________                                              Cross-                Polysul-                                                                              Sulfur, %                                       linking   Precipitant fonate  (Polysul-                                 Sample                                                                              (% DVB)   (% MAmAlc)  Conditions                                                                            fonate, %).sup.1                          ______________________________________                                        6A    12        31.5        Example 3                                                                             19.03 (111)                               6B    3.2       39.5        Example 3                                                                             --                                        6C    4         45          Example 3                                                                             --                                        6D.sup.2                                                                            20        45          Example 3                                                                             21.09 (124.6)                             6E    12        31.5        Example 2                                                                             --                                        6F    4         45          Example 2                                                                             --                                        6G    20        45          Example 2                                                                             --                                        ______________________________________                                         .sup.1 Values in parentheses are calculated as percentage of the              theoretical value for complete monosulfonation.                               .sup.2 Total pore volume above 2 nm = 0.24 ml/g; average pore diameter =      ca. 45 nm; only 4.4% of the pore volume from pores having a pore diameter     below 6 nm.                                                              

EXAMPLE 7

This example teaches the preparation of a suitable polysulfonatedprecursor from a highly crosslinked resin; it further illustrates thatpyrolysis of the polysulfonated precursor results in higher yields ofpyrolyzed polymer weight than the corresponding monosulfonatedprecursor. A macroporous polymer was prepared in suspension from highpurity (ca. 80%) divinylbenzene with no styrene added, and with 70%toluene as precipitant. The resulting polymer had a pore diameter/porevolume distribution as follows; although the pore volume between 2 and 4nm diameter (roughly the onset of the micropore range) was 16.7% of thetotal, the volume below 2 nm diameter was not measurable. The results ofthis example are in Table 4 below.

                  TABLE 4                                                         ______________________________________                                        Pore Diameter, Pore Volume,                                                   nm             cc/g.                                                          ______________________________________                                        >60            0                                                              60-40          0                                                              40-20          0.386                                                          20-10          0.492                                                          10-8           0.123                                                          8-6            0.150                                                          6-4            0.191                                                          4-2            0.269                                                          2-1            0                                                              ______________________________________                                    

The beads were polysulfonated by the method of Example 3. Particle sizeof the starting polymer was as in Example 6. The sulfur content was14.98%, which is 98.4% of the theoretical value for completemonosulfonation; in this tightly crosslinked system, it is believedpolysulfonation occurs at the surface and less-than-complete sulfonationin the interior of the particle. This sample is designated as 7A.Another sample of the highly crosslinked beads was monsulfonated withconcentrated sulfuric acid under the reaction conditions of Example 3,and is designated 7B. These samples were pyrolyzed (7B two differenttemperatures), and the yield and surface area for the pyrolyzed productsare shown in Table 5 below.

                  TABLE 5                                                         ______________________________________                                                                            BET                                               Polysul-  Pyrolysis  Yield  Surface Area                              Precursor                                                                             fonated   Temperature                                                                              %      m.sup.2 /g                                ______________________________________                                        7A      Yes       800        45.0   693                                       7B      No        800        20.8   469                                       7B      No        500        23.6   489                                       ______________________________________                                    

EXAMPLE 8

This example demonstrates the improvements in BET surface area forpolysulfonated vs. monosulfonated precursors under otherwise comparablesynthesis and pyrolysis conditions, and demonstrates the extent ofmicroporosity achieved. The polysulfonated macroporous resins ofExamples 6 and 7 were subjected to the following pyrolysis conditions:Samples were placed in a quartz tube between two quartz wool plugs, thetube purged with nitrogen, and the tube was heated to 500° C. over thecourse of approximately 1/2 hour, and held 1/2 hour. The tube was thenheated further to 800° C. over the course of 1/2 hour and held for 1/2hour. The contents of the tube were then cooled under nitrogen. Theresults of this example are in Table 6 below.

                  TABLE 6                                                         ______________________________________                                                      BET                                                                   Source  Surface  Pore Volume (cc/g)                                           of      Area     with a given pore diameter                             Sample                                                                              Resin   (m.sup.2 /g)                                                                           0.43-0.6 nm                                                                           0.6-3.5 nm                                                                            3.5-30 nm                              ______________________________________                                        8A    Ex.6A   472      0.142   0.002   0.273                                  8B    Ex.6B   222       0.0397 0       0.3086                                 8C    Ex.6C   459       0.0236 0       0.4085                                 8D    Ex.6D   521      0.218   0       0.9888                                 8E    Ex.6E   402                                                             8F    Ex.6F   381                                                             8G    Ex.6G   400                                                             8H    Ex.7A   693      0.141   0.0725  0.9173                                 8I    Ex.7B   489                                                             ______________________________________                                    

EXAMPLE 9

The examples demonstrates the determination of breakthrough volumeparameters and illustrates the improved adsorptive capacity for thepresent resins. Specific retention volume, often called breakthroughvolume, is a important parameter in gas chromatographic separation; itis the calculated volume (as liters/gram) of a gas required to passthrough a fixed weight of adsorbent bed which causes the introducedadsorbate molecules to migrate from the front edge of the bed to theback edge of the bed.

Two L-shaped, silanized glass tubes (1/4" OD×4 mm ID) were used toconnect an adsorbent tube (1/4" OD×4 mm ID×10 cm length) to the injectorand detector ports of a Varian 3700 gas chromatograph. A thermalconductivity detector was chosen to evoke responses for the adsorbates;helium was chosen as the carrier gas to improve adsorbate response. Aflow rate of 30 milliliters/minute was chosen. Adsorbent bed weights of0.200 grams were used. Elevated oven temperatures were selected whichprovided retention times (volumes) for the adsorbates ranging from 0.15to 0.75 minutes. The data obtained, as adsorbate retention volumes, wassubsequently used to construct a straight-line plot of the specificretention volume versus the reciprocal of the temperature chosen. Thisstraight line was subsequently extrapolated to obtain the value atambient temperature.

Breakthrough volumes for several common organic vapors are shown inTable 7 below; VCM=vinyl chloride.

                  TABLE 7                                                         ______________________________________                                        Pyrolysis    Specific Retention Volume, l/g                                   Sample                                                                              temp.,°                                                                           CH.sub.2 Cl.sub.2                                                                      H.sub.2 O                                                                            Ethane                                                                              VCM                                    ______________________________________                                        5A    500        1.56     0.80   0.09  1.90                                   5B    500 (1)    1.49     0.24   0.04  0.35                                   4B    800        31.5     0.10   0.20  2.52                                   4D    800 (1)    26.0     0.23   0.12  6.62                                   ______________________________________                                          (1) Control  from monosulfonated resin precursor                        

EXAMPLE 10

This example demonstrates techniques for calculating chromatographicefficiency and illustrates improved performance for the polymers of thepresent invention. The chromatographic efficiency was measured astheoretical/meter for carbon dioxide, a higher value indicating improvedseparative ability. The pyrolyzed resins were packed in a 1.83 meter by0.318 cm stainless steel column. Helium was the carrier gas at 30ml/min. The column temperature was held at 35° C. for two minutes, thenraised at a rate of 20° C./minute to a final temperature of 150° C.Injection and detector port temperatures were 200° C. A thermalconductivity detector at a sensitivity of 8×0.5 was used. The sampleconcentration was 1% for each gas present in the mixture; sample volumewas 0.6 ml. Theoretical plates for carbon dioxide were calculated as

    T.P.=5.54(t.sub.m /t.sub.r).sup.2 /L

where L=column length, t_(r) is peak width at 1/2 height, and t_(m) isretention time expressed in length. The results of this example are inTable 8 below.

                  TABLE 8                                                         ______________________________________                                        Pyrolyzed Resin                                                                             Theoretical Plates/Meter                                        ______________________________________                                        5A            574                                                             5B (control)  115                                                             4B            689                                                             4D (control)  410                                                             8A            253                                                             8D            5092                                                            ______________________________________                                    

EXAMPLE 11

This example illustrates the abiility of the polysulfonated pyrolyzedparticles effectively to separate gases. Separate samples of the resinsdescribed in Examples 4, 5, or 8 were charged to a gas chromatographicseparations tube and used as follows to separate nitrogen, carbonmonoxide, carbon dioxide, methane, acetylene, ethylene, and ethane. Withmonosulfonated sample 4D, the nitrogen and carbon monoxide are notresolved, the remaining peaks are fairly broad, and baseline separation(to allow quantification) of the two-carbon hydrocarbons is notachieved. With polysulfonated sample 4B, all peaks are sharper,qualitative separation of the CO and nitrogen peaks is observed, and thebaseline separation of all the two-carbon hydrocarbons is acceptable.With polysulfonated sample 8H, the separation of CO and nitrogen isclean and can be quantified, and all other peaks remain sharp withbaseline separation. The results of this example are in Tables 9 and 10below.

                  TABLE 9                                                         ______________________________________                                                     Theoretical                                                                   Plates      Type of                                              Example      (Plates/meter)                                                                            Sulfonation                                          ______________________________________                                        5B           111         Mono-                                                5A           492         Poly-                                                4C,D         269         Mono-                                                4A,B         673         Poly-                                                8H           1280        Poly-                                                8D           5085        Poly-                                                ______________________________________                                    

                  TABLE 10                                                        ______________________________________                                        Retention Time (min)                                                          (Peak Width at Half Height, (mm))                                                    Carbon                                                                        Mon-             Carbon Acety-                                                                              Ethyl-                                   Example                                                                              oxide   Methane  Dioxide                                                                              lene  ene   Ethane                             ______________________________________                                        5B     --      1.36     4.03   --    5.88  6.59                                              (4.5)    (6.7)  --    (U)   (U)                                5A     0.83    2.74     5.06   6.83  7.51  8.37                                      (U)     (3.9)    (4.6)  (3.5) (3.8) (5.0)                              4C,D   --      4.52     6.72   8.70  --    --                                                (.sup.˜ 7)                                                                       (7)    (U)   (U)   (U)                                4A,B   1.77    4.42     6.37   8.42  10.38 12.62                                     (U)     (3.5)    (3.9)  (5.0) (7.8) (12)                               8H     1.09    3.24     5.32   7.17  8.36  9.55                                      (U)     (2.7)    (2.5)  (2.5) .(3.0)                                                                              (5.0)                              8D     1.46    3.97     6.07   8.11  9.68  11.50                                     (1.3)   (1.3)    (1.5)  (1.5) (2.2) (4.0)                              ______________________________________                                         Note: U indicates peak was unresolved and a peak width at half height         could not be determined.                                                 

EXAMPLE 12

In a manner similar to Example 11, such resins may be for a cleanseparation of hydrogen from nitrogen for quantitative gas analysis. Thegas chromatographic conditions were those described in Example 10. Amixture of the indicated gases was used as in Example 10. The resin usedis that of Example 6D, which was polysulfonated as in Example 3,pyrolyzed at 500° C., and sieved to -20+45 mesh. The hydrogen peak onthe chromatograph was very small because of the similar filamentresponse in the thermal conductivity detector between hydrogen andhelium (carrier). The results of this example are in Table 11 below.

                  TABLE 11                                                        ______________________________________                                        Gas            Retention Time (min)                                           ______________________________________                                        Hydrogen       0.18                                                           Nitrogen       0.36                                                           Carbon Monoxide                                                                              0.67                                                           Methane        2.25                                                           Carbon Dioxide 5.25                                                           ______________________________________                                    

Baseliine separation of all of these components was achieved in thischromatogram. With use of nitrogen as a carrier, hydrogen and helium maybe separated by such a column.

EXAMPLE 13

This example demonstrates the development of mesoporosity for resinspyrolyzed at 500° C. Separate preparations duplicating polysulfonatedresins from Example 3 and 6A were pyrolyzed at 500° C. by the techniquesdescribed in Example 5. Pore size distributions are given in Table 12below.

                  TABLE 12                                                        ______________________________________                                                BET Surface                                                           Sample  Area       Pore Volume (cc/g)                                         Source  (m.sup.2 /g)                                                                             0.43-0.6 nm                                                                             0.6-3.5 nm                                                                            3.5-30 nm                                ______________________________________                                        3       517        0         0.0836  0.495                                    3 (repeat)                                                                            509        0         0.0813  0.480                                    6A      706        0         0.0704  0.311                                    ______________________________________                                    

EXAMPLE 14

This example demonstrates that further effects on the micro-andmacroporosity may be realized by the application of activationtechnology. A portion of resins of Examples 8A and 4A were screened fora profile of weight loss versus contact time under the chosen pyrolysisconditions. The actual experimental samples were then activated at 800°in an atmosphere of steam for the selected time period, then allowed tocool under nitrogen. Pore size and surface area measurements wereperformed as described above, and compared with control samples whichwere pyrolyzed but not activated. The results of this example are inTable 13 below.

                  TABLE 13                                                        ______________________________________                                                               Pore Volume (cc/g)                                                                           BET                                                            with a given pore                                                                            Surface                                       Resin   %        diameter (by nm)                                                                             Area,                                   Sample                                                                              Source  Wt. Loss 0.43-0.6                                                                             0.6-3.5                                                                             3.5-30                                                                              m.sup.2 /g                          ______________________________________                                        14A   4A      --       0.146   0.0171                                                                             0.416 512                                 14B   4A      30       0      0.362 0.559 1190                                14C   8A      --       0.130  0.002 0.273 702                                 14D   8A      15       0.0201 0.238 0.344 722                                 14E   8A      30       0      0.310 0.448 1040                                ______________________________________                                    

EXAMPLE 15

The following example demonstrates improvement in adsorptivity foractivated resins of the present invention. Samples activated by themethod of Example 14 were measured for surface area and for staticcarbon tetrachloride capacity. The static carbon tetrachloridecapacities were measured by placing weighed samples of adsorbent intared weighing bottles and measuring the weight gain by the bottles whenstored in desiccators over neat CCl₄. Uptakes were measured as afunction of activation. The results of this example are in Table 14below.

                  TABLE 14                                                        ______________________________________                                                            BET Surface                                               Adsorbent                                                                              Burn-Off   Area       CCl.sub.4 Capacity                             Source   (%)        (m.sup.2 /g)                                                                             (mg/g)                                         ______________________________________                                        Example 4A                                                                             0          495        136                                                     14.0       669        515                                                     23.2       813        597                                                     33.4       1015       673                                                     37.0       1080       1000                                           Example 8A                                                                             0          455        118                                                     12.4       629        401                                                     17.5       653        485                                                     26.1       842        617                                                     29.9       863        663                                                     37.5       910        735                                            ______________________________________                                    

EXAMPLE 16

The non-polysulfonated resin of Example 5B was activated to 15% weightloss by the method of Example 14.

EXAMPLE 17

This example shows the dynamic adsorption capacity for adsorbentsderived from polysulfonated polymers, both activated and non-activated,versus a non-polysulfonated activated control. Dynamic adsorptioncapacity was measured by passing an air stream containing a knownquantity of vapor through a column containing the pyrolyzed resin, andmeasuring the concentration of vapor in the effluent air stream using agas chromatograph with an appropriate detector.

The vapor-containing stream was produced by passing a stream of dry airthrough a closed container containing the liquid whose vapors are to beadsorbed. The vapor concentration thus produced was determined bypassing a known volume of the air-vapor mixture through a tared,activated carbon column large enough to completely adsorb all the vapor,the column being weighed after passage of the mixture to determine thetotal weight of vapor in the known volume of air.

The adsorbent resins were placed in a 1-cm. diameter glass column fittedin the middle with a coarse filtered disk; the resin sample was at a beddepth of 3.8 cm. The air-vapor mixture was passed through the column ata flow rate of 1 liter/minute, equivalent to a linear flow rate of 21cm/sec. The effluent was passed through a Hewlett-Packard Model 5880 gaschromatograph equipped with a flame ionization detector. The balance ofthe effluent was scrubbed through a bubble column of 4% sodium hydroxideand vented to an efficient hood.

Breakthrough, defined as the time at which the concentration of thechallenge vapor in the effluent stream reaches 1% of that in theinfluent stream, was determined from the gas chromatograph. Sensitivityfor the 2-chloroethyl isobutyl sulfide studied was approximately 10micrograms/liter. The results were converted to capacity in milligramsof organic vapor/gram of resin, and are shown in Table 15 below.

                  TABLE 15                                                        ______________________________________                                                                            Breakthrough                                                Polysul-          Capacity                                  Sample  Reference fonated? % Burn Off                                                                             (mg./g)                                   ______________________________________                                        17A     4A        yes       0       106                                       17B     4A        yes      14%      288                                       17C     16 .sup.  no       15%      199                                       ______________________________________                                    

The results show improved breakthrough capacity for the activated versusthe non-activated polysulfonated resin; they further show improvedbreakthrough capacity for the activated polysulfonated resin versus anon-polysulfonated resin activated to the same extent of weight loss.

EXAMPLE 18

Other challenge vapors were used in the test method of Example 17. Fordiisopropyl fluorophosphate in a humid air stream, the vaporconcentration was determined by scrubbing through a sodium hydroxidesolution with calculation of the content from the fluoride content ofthe scrub solution, using a fluoride ion electrode. In some cases, thegas chromatograph was equipped with a nitrogen-phosphorus detector.

The following vapors, when measured by the techniques described inExample 16 and 17, show enhanced breakthrough capacity for the pyrolyzedpolysulfonated resins versus a monosulfonated pyrolyzed resin startingfrom the same bead polymer, and show enhanced breakthrough when thepyrolyzed resin is further activated: methylene chloride, toluene,orthoxylene, diisopropyl fluorophosphate, and dimethylmethanephosphonate.

EXAMPLE 19

The following example shows activation of the adsorbent resin particlesof the present invention by ammonia. A pyrolyzed resin was prepared bythe process of Example 8A from the polysulfonated macroporous resin ofExample 6A. The pyrolyzed resin was then further activated by a variantof the procedure of Example 14 wherein it was treated with a stream ofgas which is 1/3 ammonia and 2/3 nitrogen at 800° C. for 1.5 hours. Theresulting particulate material, for which only 1.3% weight loss wasrealized on activation, exhibited a reduced sulfur content and anincreased nitrogen content over the non-activated resin. Such anactivated resin maintains the same surface area of the non-activatedresin when measured by BET test procedures, and is useful in separativeand adsorptive technology.

EXAMPLE 20

This example demonstrates utility of terpolymers in the presentinvention. Polymeric styrene/divinylbenzene copolymers orstyrene/divinylbenzene/trimethylpropane trimethacrylate were prepared bythe process of claim 1, were polysulfonated by the process of claim 3and were pyrolyzed by the process of claim 4. Values of surface areameasured by the technique of claim 4 are summarized below in Table 16.DVB is divinylbenzene, TMPTMA is trimethylolpropane trimethacrylate andMAmAlc is methyl amyl alcohol.

                  TABLE 16                                                        ______________________________________                                        Crosslinker        Precipitant                                                                             BET Surface                                              DVB     TMPTMA     (MAmAlc)                                                                              Area                                       Sample  (%)     (%)        (%)     (m.sup.2 /g)                               ______________________________________                                        20A     20      0          33      480                                        20B     20      0          33      498                                        20C     20      1          33      474                                        ______________________________________                                    

EXAMPLE 21

The following example describes an alternative method for thepolysulfonation and pyrolysis reaction. Polymer beads prepared as inExample 1 were polysulfonated by the method of Example 3 and pyrolyzedas in Example 4 (800° C.) or Example 5 (500° C.). Other samples of theresins prepared as in Example 1 were imbibed with 4% oleum. The oleumwas added dropwise at room temperature to dry resin with rapid stirringat a rate so that the oleum was adsorbed and the sample did not becomewet. A vacuum of about 30 mm mercury was applied throughout theaddition. About 1.8 moles of acid per mol of copolymer was added. Thesample was then heated for two hours at 50° C., and was then pyrolyzedas in Examples 4 and 5. The imbibition/pyrolysis technique, althoughless effective at producing increased BET surface area than the separatepolysulfonation/subsequent pyrolysis technique, produced polymers usefulin chromatographic and adsorptive technology. The results of thisexample are in Table 17 below.

                  TABLE 17                                                        ______________________________________                                                           Pyrolysis                                                                     Temperature,                                                                              BET Surface Area,                              Example  Technique °C.  m.sup.2 /g                                     ______________________________________                                        21A      Ex 3 and 4                                                                              800         552                                            21B      Ex 21 and 4                                                                             800         426                                            21C      Ex 3 and 5                                                                              500         574                                            21D      Ex 21 and 5                                                                             500         296                                            ______________________________________                                    

EXAMPLE 22

This example demonstrates the ability of two such pyrolyzedpolysulfonated resins to separate the noble gases. A resin similar tothat described in Example 12 (Example 22A) was packed to a 6 m by 0.32cm column. A resin (Example 22B) which was a repeat preparation ofExample 4A was sieved to -20+45 mesh and packed to a similar column. Thetemperature profile consisted of a 8 min hold at 35° C. followed byincreasing the temperature at a rate of 20° C./min to 175° C. andholding that temperature for at least 10 minutes. The carrier gasconsisted of helium except for helium peak determination which usedhydrogen as carrier. The detector was a thermal conductivity detector.The gas that was analyzed consisted of a mixture of approximately 1%each of He, H₂, Ne, O₂, N₂, Ar, CO, CH₄, CO₂, Kr and Xe. All peaks werecleanly resolved. The results of this example are shown in Table 18below.

                  TABLE 18                                                        ______________________________________                                                   Retention Time (min)                                                            6E Based   Example 4A                                                         Carbonaceous                                                                             Carbonaceous                                                       Adsorbent  Adsorbent                                             Analyte      (Ex. 22A)  (Ex. 22B)                                             ______________________________________                                        He           0.65       0.56                                                  H.sub.2      0.91       0.96                                                  Ne           1.51       3.88                                                  O.sub.2      2.32       4.72                                                  N.sub.2      2.35       4.88                                                  Ar           2.54       4.57                                                  CO           3.27       7.28                                                  CH.sub.4     9.44       13.13                                                 CO.sub.2     14.24      15.87                                                 Kr           >20.0      >20.0                                                 Xe           >20.0      >20.0                                                 ______________________________________                                    

We claim:
 1. An adsorption process which comprises contacting a liquidor gas with carbonaceous adsorbent particles which are the product ofcontrolled pyrolysis of a polysulfonated macroporous crosslinked,vinylaromatic polymer, the particles having multimodal pore-sizedistribution and a minimum micropore volume of about 0.02 cm³ /g.
 2. Aprocess for adsorbing components of a fluid which comprises treating thefluid with carbonaceous adsorbent particles which are the product ofcontrolled pyrolysis of a polysulfonated macroporous crosslinked,vinylaromatic polymer, the particles having multimodal pore-sizedistribution and a minimum micropore volume of about 0.02 cm³ /g.
 3. Theprocess of claim 2 wherein the fluid is a liquid.
 4. The process ofclaim 2 wherein the fluid is a gas.
 5. A process for adsorbingcomponents of a fluid which comprises treating the fluid withcarbonaceous adsorbent particles which are the product of controlledpyrolysis of a polysulfonated macroporous crosslinked, vinylaromaticpolymer, the particles having multimodal pore-size distribution and aminimum micropore volume of about 0.02 cm³ /g and which have beentreated, subsequent to pyrolysis, with an adsorbable, reactive agent. 6.A gas chromatographic process for separating noble gases from a gasmixture containing said noble gases which comprises passing the gasmixture through a gas-chromatographic column packed with carbonaceousadsorbent particles which are the product of controlled pyrolysis of apolysulfonated macroporous crosslinked, vinylaromatic polymer, theparticles having multimodal pore-size distribution and a minimummicropore volume of about 0.02 cm³ /g.
 7. The process of claim 6 whereinthe gas mixture containing the noble gases is air.